1. Field of the Invention
The present invention relates to methods for manufacturing amphoteric urethane resins, amphoteric resins obtained with these manufacturing methods, and resin compositions including these amphoteric urethane resins. More specifically, the present invention relates to resin compositions used for cosmetics, to methods for manufacturing amphoteric urethane resins used for such compositions, and to amphoteric urethane resins obtained with such manufacturing methods.
2. Description of the Related Art
Polyurethane resins are superior in flexibility, toughness, and abrasion resistance, and are conventionally used widely as the base in paints for buildings, wood materials and cars, for example. Furthermore, polyurethane resins have also been researched as raw material for cosmetics, and in particular, have been suggested to be useful as raw material for hair fixative.
JP H06-321741 A discloses that using an anionic urethane resin, a hair fixative with excellent hair setting properties, hair texture and hair flaking resistance can be obtained. However, anionic urethane resins have large surface-friction drag, so that in hair fixatives using anionic urethane resins, there is the problem that the touch, the luster, and the washing properties of the hair are poor.
With the object of solving this problem, JP H11-228363A discloses a resin composition for cosmetics, which includes an amphoteric urethane resin having both carboxylic groups and tertiary amino groups in each of its molecules.
Hair fixatives using a resin composition for cosmetics including such an amphoteric urethane resin attain better hair texture and washing abilities than hair fixatives including anionic urethane resins, but evaluating them by more stringent standards, the luster, the touch of the hair, and the spreadability of the hair fixative when applying the hair fixative to hair are insufficient, and a further improvement of its performance is desired. It seems that these problems are caused by the fact that the surface of the amphoteric urethane resins has a large frictional coefficient.
To solve these problems by improving the quality of the amphoteric urethane resin included in the resin composition for cosmetics, JP 2000-192476A discloses a method of introducing polysiloxane chains into the backbone of an amphoteric urethane resin by using a polysiloxane compound having functional groups including active hydrogen at one or both ends of the siloxane chain. On the other hand, JP 2001-48735A proposes a method of adding a polysiloxane compound later to an aqueous solution of an amphoteric urethane resin.
When using a hair fixative with a resin compound for cosmetics including an amphoteric urethane resin in which polysiloxane chains are introduced into the backbone (referred to as a xe2x80x9ctype 1 amphoteric urethane resinxe2x80x9d in the following) by using a polysiloxane compound having functional groups including active hydrogen at one or both ends of the siloxane chain, then the setting properties of the hair are good. However, when using a hair fixative with a resin composition for cosmetics including a type 1 amphoteric urethane resin, the spreadability of the hair fixative is insufficient.
On the other hand, when using a hair fixative with a resin compound for cosmetics including an improved amphoteric urethane resin in which the polysiloxane compound is added later to an aqueous solution of the amphoteric urethane resin (referred to as a xe2x80x9ctype 2 amphoteric urethane resinxe2x80x9d in the following), then the spreadability of the hair fixative is good. However, in type 2 amphoteric urethane resins, the polysiloxane compound added later may separate from the amphoteric urethane resin, so that there is the problem that the storage stability of cosmetics using type 2 amphoteric urethane resins is insufficient.
It is thus an object of the present invention to solve these problems and to provide a method for manufacturing an amphoteric urethane resin, in which at least one selected from the performance of paints, coating agents and cosmetics using the amphoteric urethane resin (in the case of hair fixatives, for example hair setting properties, hair texture, hair washing properties, hair touch and spreadability when applying the hair fixative), and the storage stability of the amphoteric urethane resin is improved compared to conventional amphoteric urethane resins, as well as an amphoteric urethane resin obtained with this manufacturing method and a resin composition including this amphoteric urethane resin.
In order to achieve these objects, the inventors found as the result of intensive research that by limiting the polysiloxane compound to certain compounds and limiting the time at which this certain polysiloxane compound is added when manufacturing the amphoteric urethane resin, the performance of the resulting amphoteric urethane resin is influenced, and thus conceived of the present invention.
According to one aspect of the present invention, a novel method for manufacturing an amphoteric urethane resin is provided, which uses:
(A) a polyol compound (also referred to as xe2x80x9ccompound (A)xe2x80x9d in the following);
(B) a polyisocyanate compound (also referred to as xe2x80x9ccompound (B)xe2x80x9d in the following);
(C) a polysiloxane compound (except any having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group at one or both ends of the siloxane chain) (also referred to as xe2x80x9ccompound (C)xe2x80x9d in the following);
(D) a compound having carboxyl groups and at least one selected from a hydroxyl group, a primary amino group and a secondary amino group (also referred to as xe2x80x9ccompound (D)xe2x80x9d in the following);
(E) a compound having tertiary amino groups and at least one selected from a hydroxyl group, a primary amino group and a secondary amino group (also referred to as xe2x80x9ccompound (E)xe2x80x9d in the following);
the method including:
a first step of manufacturing a prepolymer including isocyanate groups by reacting the compounds (A), (B) and (D) under the condition of excessive isocyanate groups; and
a second step of reacting the prepolymer including the isocyanate groups with the compound (E);
wherein the compound (C) is present in at least one of the first step and the second step.
According to another aspect of the present invention, another method for manufacturing an amphoteric urethane resin is provided,
which uses the compounds (A) to (E);
the method including:
a first step of manufacturing a prepolymer including isocyanate groups by reacting the compounds (A), (B) and (E) under the condition of excessive isocyanate groups; and
a second step of reacting the prepolymer including the isocyanate groups with the compound (D);
wherein the compound (C) is present in at least one of the first step and the second step.
Thus, in the manufacturing methods of the present invention, the order in which the compound (D) and the compound (E) are reacted can be inverted.
One feature of the manufacturing method of the present invention is that the compound (C) is present in at least one of the first step and the second step. Here, the compound (C) can be present at any time during the first step and the second step, and the compound (C) does not necessarily have to be present from the start of the reaction. The compound (C) should be present by the time the reaction product of the second step is mixed with water. Consequently, in this specification, xe2x80x9cfirst stepxe2x80x9d means the time from the beginning of the reaction of the first step to the beginning of the reaction of the second step, and xe2x80x9csecond stepxe2x80x9d means the time from the beginning of the reaction of the second step to the subsequently performed step (more specifically, until the reaction product of the second step explained below is mixed with water).
A feature of the manufacturing method of the present invention is that the compound (C) is xe2x80x9cpresentxe2x80x9d in at least one of the first step and the second step. Here, xe2x80x9cpresentxe2x80x9d means that the compound (C) is present in the reaction system, and although it is not intended to actively react the compound (C), eventually a portion of the compound (C) may inevitably be reacted. That is to say, the manufacturing method of the present invention, intends to xe2x80x9cconstrainxe2x80x9d the compound (C) with the backbone of the amphoteric urethane resin, or to xe2x80x9centanglexe2x80x9d the compound (C) with the backbone of the amphoteric urethane resin, and it does not intend to chemically react the compound (C) actively with the backbone of the amphoteric urethane resin. However, the compound (C) can eventually also form a portion of the backbone of the amphoteric urethane resin, and as long as the desired amphoteric urethane resin can be obtained, this is also included in the manufacturing method of the present invention. Consequently, xe2x80x9camphoteric urethane resinxe2x80x9d according to the present invention means an amphoteric urethane resin in which the compound (C) is xe2x80x9cconstrained byxe2x80x9d and/or xe2x80x9centangled withxe2x80x9d the backbone of the amphoteric urethane resin, but it can also be an amphoteric urethane resin, in which a portion of the backbone of the amphoteric urethane resin stems from the compound (C). The intention of the present invention is explained in more detail further below.
According to another aspect of the present invention, a novel method for manufacturing an amphoteric urethane resin is provided,
which uses the compounds (A) to (E), and
(F) compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group, and structural units indicated by the following formula (11)
xe2x80x94(C2H4O)p(C3H6O)qxe2x80x94xe2x80x83xe2x80x83(11) 
wherein xe2x80x9cpxe2x80x9d is an integer of 1 to 500, xe2x80x9cqxe2x80x9d is an integer of 0 to 400, and
wherein, if the structural units in structural formula (11) are copolymers of C2H4O and C3H6O (that is, qxe2x89xa00), then they can be random copolymers or block copolymers (also referred to as xe2x80x9ccompound (F)xe2x80x9d in the following);
the method comprising:
a first step of manufacturing a prepolymer including isocyanate groups by reacting the compounds (A), (B), (D) and (F) under the condition of excessive isocyanate groups; and
a second step of reacting the prepolymer including the isocyanate groups with the compound (E);
wherein the compound (C) is present in at least one of the first step and the second step.
According to yet another aspect of the present invention, another method for manufacturing an amphoteric urethane resin is provided,
which uses the compounds (A) to (F);
the method comprising:
a first step of manufacturing a prepolymer including isocyanate groups by reacting the compounds (A), (B), (E) and (F) under the condition of excessive isocyanate groups; and
a second step of reacting the prepolymer including the isocyanate groups with the compound (D);
wherein the compound (C) is present in at least one of the first step and the second step.
Thus, in the manufacturing methods of the present invention, the order in which the compound (D) and the compound (E) are reacted can be inverted. Moreover, xe2x80x9cpresentxe2x80x9d, xe2x80x9cfirst stepxe2x80x9d, and xe2x80x9csecond stepxe2x80x9d are as explained above.
In the manufacturing method in accordance with the present invention, it is preferable that after the second step, a chain-extending reaction is performed by mixing the reaction product of the second step with water.
In the manufacturing method in accordance with the present invention, it is also preferable that after the second step, a chain-extending reaction is performed by mixing the reaction product of the second step with alkaline water, or a chain-extending reaction is performed by adding an alkaline compound to the reaction product of the second step, and then mixing it with water.
The present invention also presents an amphoteric urethane resin obtained by the manufacturing method of the present invention, as well as an aqueous solution of such an amphoteric urethane resin and a resin composition including such an amphoteric urethane resin.
The resin composition according to the present invention can be used, for example, as paint for buildings, wood materials and cars, as a coating agent or for cosmetics, but it is particularly useful as a resin composition for cosmetics.
In this specification, xe2x80x9c(A) polyol compoundxe2x80x9d refers to polyol compounds that are commonly used to manufacture urethane resins, and there is no particular limitation. Examples of such compounds (A) include polyester polyols, polyether polyols, polycarbonate polyols, polybutadiene polyols, polyisoprene polyols, polyolefin polyols, and polyacrylate polyols.
It is particularly preferable to use a polyester polyol or a polyether polyol as the compound (A).
Examples of xe2x80x9cpolyester polyolsxe2x80x9d include polyester polyols obtained by condensation polymerization of at least one kind of dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, and terephthalic acid, and at least one kind of polyhydric alcohol such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexadiol, neopentyl glycol, 1,8-octanediol, 1,10-decanediol, diethylene glycol, spiroglycol, and trimethylol propane, as well as polyester polyols obtained by ring-opening polymerization of lactones.
As xe2x80x9cpolyether polyolsxe2x80x9d, it is possible to use, polyether polyols obtained by ring-opening addition polymerization of water, polyhydric alcohols used for the synthesis of the above-mentioned polyester polyols, phenols such as bisphenol A, their hydrides, or primary amines or secondary amines, with such cyclic ethers as ethylene oxide, propylene oxide, oxetane and tetrahydrofuran. Further examples include polyoxypropylene polyol, polyoxytetramethylene polyol, as well as polyether polyols obtained by ring-opening addition polymerization of at least one of propylene oxide and ethylene oxide with bisphenol A (in case of a copolymer, either a block copolymer or a random copolymer is possible).
Other examples for the compound (A) include LMW polyol compounds, such as 1,4-cyclohexane dimethanol, ethylene glycol, propylene glycol, isopropylene glycol, 1,4-butanediol, 1,3-butanediol, butylene glycol, 1,6-hexadiol, neopentyl glycol, 1,8-octanediol, 1,10-decanediol, diethylene glycol, dipropylene glycol, spiroglycol, trimethylol propane, glycerine, diglycerine, and triglycerine.
It is preferable to use 1,4-cyclohexane dimethanol for the compound (A).
The compound (A) can be used alone or in combination.
Throughout this specification, if a compound of the compounds (A) overlaps with the compounds (F) explained below, then that compound is included in the compounds (F) and not included in the compounds (A).
Also, throughout this specification, if a compound of the compounds (A) overlaps with the compounds (D) explained below, then that compound is included in the compounds (D) and not included in the compounds (A).
And, throughout this specification, if a compound in the compounds (A) overlaps with the compounds (E) explained below, then that compound is included in the compounds (E) and not included in the compounds (A).
xe2x80x9c(B) polyisocyanate compoundxe2x80x9d refers to polyisocyanate compounds that are commonly used to manufacture urethane resins, and there is no particular limitation. Examples of such compounds (B) include organic diisocyanate compounds, such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds.
Examples of xe2x80x9caliphatic diisocyanate compoundsxe2x80x9d include ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 1,6-hexamethylene diisocyanate.
Examples of xe2x80x9calicyclic diisocyanate compoundsxe2x80x9d include hydrogenated 4,4xe2x80x2-diphenylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, and norbornane diisocyanate. Examples of xe2x80x9caromatic diisocyanate compoundsxe2x80x9d include 4,4xe2x80x2-diphenylmethane diisocyanate, xylylene diisocyanate, toluene diisocyanate, and naphthalene diisocyanate.
1,6-hexamethylene diisocyanate, isophorone diisocyanate, and norbornane diisocyanate are preferable because of their excellent weather resistance and their low cost.
The compound (B) can be used alone or in combination.
xe2x80x9c(C) polysiloxane compound (except any having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group at one or both ends of the siloxane chain)xe2x80x9d refers to polysiloxane compounds, but not to polysiloxane compounds that have at least one selected from a hydroxyl group (xe2x80x94OH), a primary amino group (xe2x80x94NH2) and a secondary amino group (xe2x80x94NHxe2x80x94) at one or both ends of the siloxane chain, and there is no particular limitation, as long as the desired amphoteric urethane resin can be obtained.
Consequently, the compound (C) includes polysiloxane compounds having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group at portions other than the ends of the siloxane chain (or at a center portion of the siloxane chain), as well as polysiloxane compounds not having any hydroxyl group, primary amino group or secondary amino group at all.
Examples of the compound (C) include at least one selected from polydimethyl siloxane, polyether-modified silicone, cyclic silicone, phenyl-modified silicone, alkyl-modified silicone, and alkoxy-modified silicone.
An example of a xe2x80x9cpolydimethyl siloxanexe2x80x9d is given by the compound illustrated by the general formula (21) below. 
In formula (21), xe2x80x9cnxe2x80x9d is an integer of one or greater.
It is preferable that the xe2x80x9cnxe2x80x9d in formula (21) is an integer of 1 to 100, more preferably an integer of 1 to 50, and most preferably an integer of 3 to 30.
Examples of a xe2x80x9cpolydimethyl siloxanexe2x80x9d include the SH200(trademark) series by Dow Corning Toray Silicone Co., Ltd. and the KF96(trademark) series by Shin-Etsu Chemical Co., Ltd.
An example of a xe2x80x9cpolyether-modified siliconexe2x80x9d is given by the compound illustrated by the general formula (22) below. 
In formula (22), xe2x80x9cmxe2x80x9d is an integer of zero or greater and xe2x80x9cnxe2x80x9d is an integer of one or greater.
R21 is the group illustrated by formula (22-2) below:
xe2x80x94(CH2)axe2x80x94(OC2H4)bxe2x80x94(OC3H6)cxe2x80x94OR22xe2x80x83xe2x80x83(22-2) 
In Formula (22-2), R22 is a hydrogen atom or a hydrocarbon group with a carbon number of 1 to 10.
xe2x80x9caxe2x80x9d is an integer of 1 to 10, xe2x80x9cbxe2x80x9d is an integer of 1 to 300, and xe2x80x9ccxe2x80x9d is an integer of 0 to 300.
In formula (22), it is preferable that xe2x80x9cmxe2x80x9d is an integer of 1 to 300, more preferably an integer of 1 to 100, and most preferably an integer of 1 to 50. xe2x80x9cnxe2x80x9d is preferably an integer of 1 to 300, more preferably an integer of 1 to 100, and most preferably an integer of 1 to 50.
In formula (22-2), xe2x80x9caxe2x80x9d is preferably an integer of 1 to 5, and more preferably an integer of 2 to 4. xe2x80x9cbxe2x80x9d is preferably an integer of 2 to 50, more preferably an integer of 2 to 40, and most preferably an integer of 2 to 30. xe2x80x9ccxe2x80x9d is preferably an integer of 0 to 50, more preferably an integer of 0 to 40, and most preferably an integer of 0 to 30.
For the compound (C), it is preferable that in formula 22, xe2x80x9cmxe2x80x9d is an integer of 1 to 300, xe2x80x9cnxe2x80x9d is an integer of 1 to 300, R21 is the group illustrated by formula (22-2), xe2x80x9caxe2x80x9d is an integer of 1 to 5, xe2x80x9cbxe2x80x9d is an integer of 2 to 50, and xe2x80x9ccxe2x80x9d is an integer of 0 to 50.
For the compound (C), it is more preferable that in formula 22, xe2x80x9cmxe2x80x9d is an integer of 1 to 100, xe2x80x9cnxe2x80x9d is an integer of 1 to 100, R21 is the group illustrated by formula (22-2), xe2x80x9caxe2x80x9d is an integer of 2 to 4, xe2x80x9cbxe2x80x9d is an integer of 2 to 40, and xe2x80x9ccxe2x80x9d is an integer of 0 to 40.
For the compound (C), it is most preferable that in formula 22, xe2x80x9cmxe2x80x9d is an integer of 1 to 50, xe2x80x9cnxe2x80x9d is an integer of 1 to 50, R21 is the group illustrated by formula (22-2), xe2x80x9caxe2x80x9d is an integer of 2 to 4, xe2x80x9cbxe2x80x9d is an integer of 2 to 30, and xe2x80x9ccxe2x80x9d is an integer of 0 to 30.
Examples of the compound illustrated by formula (22) include SH3746(trademark), SH3771C(trademark), SH3772C(trademark), SH3773C(trademark), SH3775C(trademark), SH3748(trademark), SH3749(trademark), SH3771M(trademark), SH3772M(trademark), SH3773M(trademark) and SH3775M(trademark) by Dow Corning Toray Silicone Co., Ltd. and KF351A(trademark), KF353A(trademark), KF945A(trademark), KF352A(trademark), KF615A(trademark), KF6011(trademark), KF6012(trademark), KF6013(trademark), KF6015(trademark), KF6016(trademark) and KF6017(trademark) by Shin-Etsu Chemical Co., Ltd.
An example of a xe2x80x9cphenyl-modified siliconexe2x80x9d is given by the compound illustrated by the general formula (23) below. 
In formula (23), R25 and R26 are hydrocarbon groups with a carbon number of 1 to 12 (for example, straight-chained or branched saturated hydrocarbon groups with a carbon number of 1 to 12), xe2x80x94OSi(CH3)3 or phenyl groups, and R25 and R26 can be the same or different. However, at least one of R25 and R26 is a phenyl group.
xe2x80x9cmxe2x80x9d is an integer of zero or greater, and xe2x80x9cnxe2x80x9d is an integer of one or greater.
In formula (23), it is preferable that xe2x80x9cmxe2x80x9d is an integer of 0 to 300, more preferably an integer of 0 to 100, and most preferably an integer of 0 to 50. xe2x80x9cnxe2x80x9d is preferably an integer of 1 to 500, more preferably an integer of 1 to 100, and most preferably an integer of 1 to 50.
For the phenyl-modified silicone, a methylphenyl polysiloxane as in formula (23) with R25=CH3 or xe2x80x94OSi(CH3)3, R26=C6H5, m=0, n=1 to 100 is particularly preferable.
Examples of phenyl-modified silicones include SH556(trademark), SF557(trademark), SF558(trademark) and SH559(trademark) by Dow Corning Toray Silicone Co., Ltd. and KF50-100cs(trademark), KF50-1000cs(trademark), KF53(trademark), KF54(trademark), and KF56(trademark) by Shin-Etsu Chemical Co., Ltd.
An example of an xe2x80x9calkyl-modified siliconexe2x80x9d is given by the compound illustrated by the general formula (24) below. 
In formula (24), R27 to R29 are hydrocarbon groups with a carbon number of 1 to 50, which can be the same or different. However, at least one of R27 to R29 is a hydrocarbon group with a carbon number of 5 to 30.
xe2x80x9cmxe2x80x9d is an integer of one or greater, and xe2x80x9cnxe2x80x9d is an integer of one or greater.
In formula (24), R27 to R29 are hydrocarbon groups with a carbon number of 1 to 50, for example straight-chained or branched saturated hydrocarbon groups. It is preferable that the hydrocarbon groups have a carbon number of 5 to 30, more preferably of 5 to 20, and most preferably of 10 to 20.
Moreover, xe2x80x9cmxe2x80x9d is preferably an integer of 1 to 300, more preferably an integer of 1 to 100, and most preferably an integer of 1 to 50. xe2x80x9cnxe2x80x9d is preferably an integer of 1 to 300, more preferably an integer of 1 to 100, and most preferably an integer of 1 to 50.
Examples of the alkyl-modified silicone include SF8416(trademark) by Dow Corning Toray Silicone Co., Ltd. and KF-412(trademark), KF-413(trademark) and KF-414(trademark) by Shin-Etsu Chemical Co., Ltd.
An example of an xe2x80x9calkoxy-modified siliconexe2x80x9d is given by the compound illustrated by the general formula (25) below. 
In formula (25), R30 to R32 are hydrocarbon groups with a carbon number of 1 to 12, or alkoxy groups with a carbon number of 1 to 50, and R30 to R32 can be the same or different. However, at least one of R30 to R32 is an alkoxy group with a carbon number of 1 to 50.
xe2x80x9cmxe2x80x9d is an integer of zero or greater, and xe2x80x9cnxe2x80x9d is an integer of one or greater.
In formula (25), R30 to R32 are hydrocarbon groups with a carbon number of 1 to 12, or alkoxy groups with a carbon number of 1 to 50, and examples of hydrocarbon groups with a carbon number of 1 to 12 include straight-chained and branched saturated hydrocarbon groups, whereas examples of alkoxy groups with a carbon number of 1 to 50 include straight-chained and branched alkoxy groups. The carbon number of the alkoxy groups with a carbon number of 1 to 50 is preferably 1 to 30, more preferably 1 to 25, and most preferably 1 to 20.
xe2x80x9cmxe2x80x9d is preferably an integer of 1 to 500, more preferably an integer of 1 to 100, and most preferably an integer of 1 to 50. xe2x80x9cnxe2x80x9d is preferably an integer of 1 to 100, more preferably an integer of 1 to 80, and most preferably an integer of 1 to 50.
Examples of xe2x80x9calkoxy-modified siliconesxe2x80x9d include KF-851(trademark) and X-22-801(trademark) by Shin-Etsu Chemical Co., Ltd.
An example of a xe2x80x9ccyclic siliconexe2x80x9d is given by the compound illustrated by the general formula (26). 
In formula (26), R33 denotes a hydrocarbon group with a carbon number of 2 to 12, wherein the repeating units can be the same or different
xe2x80x9cmxe2x80x9d is an integer of one or greater, and xe2x80x9cnxe2x80x9d is an integer of zero or greater, and the sum of xe2x80x9cmxe2x80x9d and xe2x80x9cnxe2x80x9d (m+n) is 3 to 10.
In formula (26), R33 is a hydrocarbon group with a carbon number of 2 to 12, for example a straight-chained or branched saturated hydrocarbon group. R33 has a carbon number of preferably 2 to 10, more preferably of 2 to 8, and most preferably of 2 to 5.
xe2x80x9cmxe2x80x9d is preferably an integer of 3 to 8, more preferably an integer of 4 to 8, and most preferably an integer of 4 to 6. xe2x80x9cnxe2x80x9d is preferably an integer of 0 to 7, more preferably an integer of 0 to 5, and most preferably an integer of 0 to 3. The sum of xe2x80x9cmxe2x80x9d and xe2x80x9cnxe2x80x9d (m+n) is preferably 3 to 8, more preferably 4 to 8 and most preferably 4 to 6.
Examples of cyclic silicones include SH244(trademark), SH344(trademark), SH245(trademark), DC345(trademark) and DC246(trademark) by Dow Corning Toray Silicone Co., Ltd. and KF994(trademark), KF995(trademark) and KF9937(trademark) by Shin-Etsu Chemical Co., Ltd.
The repeating units in the compounds shown in the formulas (22) to (26) can be of any polymer type, such as random polymers or block polymers.
The viscosity (dynamic viscosity) of the compound (C) at 25xc2x0 C. is preferably 1 to 5000 mm2/s, more preferably 1 to 2000 mm2/s, and most preferably 1 to 1000 mm2/s.
For the compound (C), polydimethyl siloxanes and polyether-modified silicones are preferable.
The compound (C) can be used alone or in combination. xe2x80x9c(D) compound having carboxyl groups and at least one selected from a hydroxyl group, a primary amino group and a secondary amino groupxe2x80x9d refers to a compound containing at least one selected from a hydroxyl group, a primary amino group and a secondary amino group, and at least one carboxyl group in its molecules, and there is no particular limitation, as long as the desired amphoteric urethane resin can be obtained with that compound.
Examples of the compound (D) include dimethylolpropanoic acid, dimethylolbutanoic acid, and polycaprolactone diol including carboxylic groups.
The compound (D) can be used alone or in combination.
xe2x80x9c(E) compound having tertiary amino groups, and at least one selected from a hydroxyl group, a primary amino group and a secondary amino groupxe2x80x9d refers to a compound containing at least one selected from a hydroxyl group, a primary amino group and a secondary amino group, and at least one tertiary amino group in its molecules, and there is no particular limitation, as long as the desired amphoteric urethane resin can be obtained with that compound.
Examples of the compound (E) include N-alkyldialkanolamine compounds, such as N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine, N-methyldipropanolamine, and N,N-dialkylalkanolamine compounds, such as N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, as well as triethanolamines.
The compound (E) can be used alone or in combination.
It is preferable that the weight ratio of the compound (C) to the compounds (A), (B), (D) and (E), i.e. (C)/((A)+(B)+(D)+(E)) is 0.1/100 to 30/100, more preferably 0.5/100 to 25/100, and most preferably 1/100 to 20/100.
Moreover, the mole ratio of compound (B) to compounds (A), (D) and (E), i.e. (B)/((A)+(D)+(E)) is preferably 2.0/0.8 to 2.0/1.8, more preferably 2.0/1.0 to 2.0/1.8, and most preferably 2.0/1.2 to 2.0/1.8.
A method for manufacturing an amphoteric urethane resin in accordance with the present invention includes:
a first step of manufacturing a prepolymer including isocyanate groups by reacting the above-described compounds (A), (B) and (D) under the condition of excessive isocyanate groups, and
a second step of reacting the prepolymer including the isocyanate groups with the compound (E),
wherein the compound (C) is present in at least one of the first step and the second step.
In another method for manufacturing the amphoteric urethane resin according to the present invention, the order in which the compound (E) and the compound (D) are reacted is inverted.
The reactions of the first step and the second step can be carried out with suitable polymerization catalysts and under reaction conditions that are ordinarily used to manufacture polyurethanes.
As a xe2x80x9cpolymerization catalystxe2x80x9d, it is possible to use any polymerization catalyst that is ordinarily used to manufacture urethane resins. There is no particular limitation with regard to the polymerization catalyst, as long as the desired amphoteric urethane resin can be obtained. It is possible to use, for example, a tertiary amine catalyst or an organic metal catalyst for the xe2x80x9cpolymerization catalystxe2x80x9d. Examples of xe2x80x9ctertiary aminesxe2x80x9d include [2,2,2]-diazabicyclooctane (DABCO), tetramethylenediamine, N-methylmorpholine, and diazabicycloundecene (DBU). Examples of xe2x80x9corganic metal catalystsxe2x80x9d include dibutyltindilaurate.
In all of the manufacturing methods of the present invention, an organic solvent can be used as necessary for the reactions of the first step and the second step. It is particularly preferable to use an organic solvent that can dissolve the compounds (A) to (E) as well as the urethane resin to be created. Examples of such an organic solvent include amides, such as N-methyl-pyrolidine, dimethylformamide, and dimethylacetoamide, ketones, such as acetone, and methylethylketone, esters, such as ethyl acetate, and cellosolve acetate or cellosolve ether.
Furthermore, in the manufacturing methods according to the present invention, it is preferable to mix, after the second step, the reaction product of the second step with water to carry out a chain-extending reaction.
In the manufacturing methods according to the present invention, it is preferable that, after the second step, the chain-extending reaction is performed by mixing the reaction product of the second step with alkaline water, or by adding an alkaline compound to the reaction product of the second step and then mixing it with water. It is more preferably to perform the chain-extending reaction by mixing the reaction product of the second step with alkaline water.
Here, xe2x80x9calkaline waterxe2x80x9d refers to water, in which an alkaline substance has been dissolved, so that the water has alkalinity. Examples of alkaline water include water in which, for example, triethylamine, triethanolamine, ammonia, sodium hydroxide, potassium hydroxide or 2-amino-2-methyl-1-propanol has been dissolved.
It is preferable to perform a chain-extending reaction in the manufacturing method of the present invention. In the chain-extending reaction, it is possible to use a chain-extending agent, and it is possible to adjust the properties of the finally obtained amphoteric urethane resin with this chain-extending reaction.
A xe2x80x9cchain-extending agentxe2x80x9d is a compound that is used for a chain-extending reaction. Examples of chain-extending agents include LMW polyols, amines and water. Examples of LMW polyols include glycols, such as ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexadiol, spiroglycol, bis(P-hydroxyethoxy)benzene, and xylylene glycol, as well as triols, such as trimethylolpropane and glycerin. Examples of xe2x80x9caminesxe2x80x9d include methylene(bis-o-chloraniline).
In the method for manufacturing an amphoteric urethane resin in accordance with the present invention, it is preferable that, after the second step, the reaction product of the second step is mixed with alkaline water to perform a chain-extending reaction in water.
Furthermore, in the method for manufacturing an amphoteric urethane resin in accordance with the present invention, it is preferable that, after the reactions of the first step and the second step have been performed in an organic solvent, the reaction mixture after the second step is mixed with alkaline water, and subsequently the chain-extending reaction is performed in the water.
This configuration of mixing the reaction mixture after the second step with alkaline water, and subsequently performing the chain-extending reaction in water is preferable, because this way, an amphoteric urethane resin of high molecular weight can be obtained easily. In the manufacturing method of this configuration, it is preferable that the manufacturing conditions are set such that the reaction mixture after the second step is a prepolymer including isocyanate groups at its chain ends.
In the manufacturing method of the present invention, a manufacturing method is presented, which uses, in addition to the compounds (A) to (E), xe2x80x9c(F) compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group, and structural units indicated by the following formula (11)
xe2x80x94(C2H4O)p(C3H6O)qxe2x80x94xe2x80x83xe2x80x83(11) 
wherein xe2x80x9cpxe2x80x9d is an integer of 1 to 500, xe2x80x9cqxe2x80x9d is an integer of 0 to 400, and if the structural units in formula (11) are copolymers of C2H4O and C3H6O (that is qxe2x89xa00), then they can be random copolymers or block copolymers (referred to as xe2x80x9ccompound (F)xe2x80x9d in the following).
The compound (F) is a compound having xe2x80x9cat least one selected from a hydroxyl group, a primary amino group and a secondary amino group, and structural units indicated by the formula (11)xe2x80x9d, and there is no limitation with regard to the compound (F), as long as the desired amphoteric urethane resin can be obtained.
If in the formula (11) q=0, then the structural units shown by the formula (11) forms a C2H4 polymer (polyoxyethylene), and if qxe2x89xa00, then they form a copolymer of C3H6O and C2H4O. In the case of copolymers of C3H6O and C2H4O, the structural units shown in formula (11) can be random copolymers or block copolymers, and are not limited by the arrangement of C2H4O and C3H6O.
In formula (11), regardless whether qxe2x89xa00 or q=0, xe2x80x9cpxe2x80x9d is preferably 3 to 250, more preferably 3 to 120, and most preferably 3 to 50.
If xe2x80x9cpxe2x80x9d is less than 3, then the compound (F) does not contain enough C2H4O and it may be difficult to provide the amphoteric urethane resin with enough hydrophilicity. Consequently, if the amphoteric urethane resin is used as hair fixative, the hydrophilicity and hair-washing properties of the hair fixative may be insufficient. If xe2x80x9cpxe2x80x9d is larger than 500, then the compound (F) contains too much C2H4O, so that the amphoteric urethane resin is provided with too much hydrophilicity. Consequently, the hydrophilicity of the hair fixative may be too strong, and if the amphoteric urethane resin is used as hair fixative, the moisture resistance of the hair may decrease.
If in formula (11) qxe2x89xa00, then xe2x80x9cqxe2x80x9d is preferably 3 to 200, more preferably 3 to 100, and most preferably 3 to 40.
In formula (11), regardless whether qxe2x89xa00 or q=0, p+q is preferably 3 to 300, more preferably 10 to 120, and most preferably 3 to 50.
In formula (11), regardless whether qxe2x89xa00 or q=0, the weight ratio between C2H4O and C3H6O (i.e. C2H4O/C3H6O) is preferably 10/0 to 2/8 more preferably 10/0 to 3/7, and most preferably 10/0 to 4/6.
Regarding the structural units shown by formula (11), it is preferable that q=0.
It is preferable that the compound (F) is of the type with OH groups introduced at both ends, the type with NH2 groups introduced at both ends, the type with an OH group introduced at one end, or of the type with an NH2 group introduced at one end. If a compound (F) of the type with OH groups introduced at both ends or the type with NH2 groups introduced at both ends is used, then an amphoteric urethane resin is obtained, that has the structural units shown in formula (11) within the principal chain. If a compound (F) of the type with an OH group introduced at one end or of the type with an NH2 group introduced at one end is used, then an amphoteric urethane resin is obtained, that has the structural units shown in formula (11) in a side chain or at the chain end.
The weight-average molecular weight of the compound (F) is preferably 200 to 20000, more preferably 200 to 5000, and most preferably 500 to 2000.
Examples of the compound (F) include polyethyleneglycol (PEG) and polyethylene-polypropylene glycol (polyethylene-polypropylene block copolymer), but polyethyleneglycol (or polyoxyethylene polyol) is preferable.
The compound (F) can be used alone or in combination.
Consequently, the present invention provides a method for manufacturing an amphoteric urethane resin, including
a first step of manufacturing a prepolymer including isocyanate groups by reacting the compounds (A), (B), (D) and (F) under the condition of excessive isocyanate groups, and
a second step of reacting the prepolymer including the isocyanate groups with the compound (E),
wherein the compound (C) is present in at least one of the first step and the second step.
The present invention also provides a method for manufacturing an amphoteric urethane resin, including
a first step of manufacturing a prepolymer including isocyanate groups by reacting the compounds (A), (B), (E) and (F) under the condition of excessive isocyanate groups, and
a second step of reacting the prepolymer including the isocyanate groups with the compound (D),
wherein the compound (C) is present in at least one of the first step and the second step.
The reactions of the first step and the second step to which the compound (F) has been added can be carried out similarly as the afore-mentioned first and second step, can be carried out with suitable polymerization catalysts and under reaction conditions that are ordinarily used to manufacture polyurethanes.
The xe2x80x9cpolymerization catalystxe2x80x9d, xe2x80x9corganic solventxe2x80x9d, xe2x80x9cchain-extending agentxe2x80x9d etc. can be as described above, and when the compound (F) is added, it is preferable that the first step and the second step are carried out in an organic solvent, and the chain-extending reaction is carried out in water.
The weight ratio of the compound (C) and the compounds (A), (B), and (D) to (F), i.e. (C)/((A)+(B)+(D)+(E)+(F)) is preferably 0.1/100 to 30/100, more preferably 0.5/100 to 25/00, and most preferably 1/100 to 20/100.
The mole ratio of the compound (B) and the compounds (A), (D), (E) and (F), i.e. (B)/((A)+(D)+(E)+(F)) is preferably 2.0/0.8 to 2.0/1.8, more preferably 2.0/1.0 to 2.0/1.8, and most preferably 2.0/1.2 to 2.0/1.8.
The present invention provides an amphoteric urethane resin that is obtained by the above-described manufacturing methods.
The amphoteric urethane resin obtained with the manufacturing methods according to the present invention has carboxylic groups and tertiary amino groups in each molecule. The ratio between carboxylic groups and tertiary amino groups (the ratio between the number of both functional groups), i.e. carboxylic groups/tertiary amino groups, is preferably 1/50 to 50/1, more preferably 1/1 to 50/1, and most preferably 1/1 to 25/1. If the ratio between carboxylic groups and tertiary amino groups in the amphoteric urethane resin is 1/50 to 50/1, then the hair can be provided with a more pleasant texture when using it for a hair fixative with a resin composition including an amphoteric urethane resin, or in the case of a paint or coating with a resin composition including the amphoteric urethane resin, better adhesion to the substrate can be attained.
In the manufacturing method of the present invention, the ratio (mole ratio) between the compounds (D) and (E), i.e. compound (D)/compound (E), is preferably 1/50 to 50/1, more preferably 1/1 to 50/1, and most preferably 1/1 to 25/1.
The amphoteric urethane resin according to the present invention is preferably used in form of an aqueous solution, and it is preferable that the amphoteric urethane resin according to the present invention forms an aqueous solution when mixed with water. In this specification xe2x80x9caqueous solutionxe2x80x9d refers not only to aqueous solutions in which the amphoteric urethane resin is completely dissolved in water, but also to aqueous dispersions and/or aqueous suspensions in which the amphoteric urethane resin is dispersed and/or suspended in water. The present invention provides an aqueous solution of the amphoteric urethane resin according to the present invention.
However, it is also possible to use the resin component of the amphoteric urethane resin obtained by practically eliminating the solvent.
In this specification, xe2x80x9cwaterxe2x80x9d means any kind of water, and includes distilled water, ion exchanged water, and pure water. Furthermore, within a range that does not adversely affect the manufacturing and the quality of the desired amphoteric urethane resin, the xe2x80x9cwaterxe2x80x9d can also include organic solvents, monomers, etc. that are soluble or dispersible in water.
The present invention presents a resin composition including the above-described amphoteric urethane resin. Here, xe2x80x9cresin compositionxe2x80x9d means compositions including various additives that are commonly added to urethane resins. Examples of such xe2x80x9cadditivesxe2x80x9d include pigments, dyes, coloring agents, perfumes, surfactants, moisturizing agents, preservatives, disinfectants, antiseptics, antioxidants, thickeners, and pH-adjusting agents. It is preferable that also the xe2x80x9cresin compositionxe2x80x9d is used in form of an aqueous solution. Needless to say, it is also possible to subject the xe2x80x9cresin compositionxe2x80x9d to additional processing, such as adding other additives, and, depending on its purpose, subject it to other modifications, as suitable.
The xe2x80x9camphoteric urethane resinxe2x80x9d and the xe2x80x9cresin composition including an amphoteric urethane resinxe2x80x9d according to the present invention can be used for any field in which urethane resins are ordinarily used, such as cosmetics, paints, and coating agents, for example. It is preferable to use them for cosmetics. Examples of xe2x80x9ccosmeticsxe2x80x9d include hair fixatives, coating agents, and viscosity modifiers. Examples of xe2x80x9chair fixativesxe2x80x9d include hair fixatives in form of foams, gels, aerosol sprays, and pump sprays. Examples of xe2x80x9ccoating agentsxe2x80x9d and xe2x80x9cviscosity modifiersxe2x80x9d include conditioning/shaving/creaming agents, skin care lotions, emulsified foundations, cream foundations, eyeliners, mascaras, nail color, and packs.
With the amphoteric urethane resin according to the present invention, at least one effect selected from improving the performance of paints, coating agents and cosmetics using the amphoteric urethane resin according to the present invention and improving the storage stability of the amphoteric urethane resin compared to conventional amphoteric urethane resins is achieved, and it is particularly superior in cosmetics. This seems to be due to the following reasons.
The amphoteric urethane resin according to the present invention does not necessarily include polysiloxane chains of the polysiloxane compound (C) through covalent bonds in its backbone, and it seems that the amphoteric urethane resin includes polysiloxane chains by entangling its backbone physically with the polysiloxane chains of the polysiloxane compound (C). This mutual entanglement is further complicated by the proceeding polymerization reaction of the amphoteric urethane, and it seems to be difficult to separate the polysiloxane compounds from the obtained amphoteric urethane resin.
In this specification, the entanglement of the backbone of the amphoteric urethane resin and the polysiloxane compounds is referred to as a state in which the backbone of the amphoteric urethane resin xe2x80x9cconstrainsxe2x80x9d the polysiloxane compounds. Here, xe2x80x9cconstraintxe2x80x9d differs depending on whether the amphoteric urethane resin is in form of an aqueous solution or in form of an aqueous dispersion. The backbone of the amphoteric urethane resin has usually a straight-chain structure, but it can also have a branched structure or a cross-linked structure. If the amphoteric urethane resin is in form of an xe2x80x9caqueous solutionxe2x80x9d, then it seems that polysiloxane chains enter the backbone of the amphoteric urethane resin.
On the other hand, if the amphoteric urethane resin is in the form of an xe2x80x9caqueous dispersionxe2x80x9d, then it seems that the amphoteric urethane resin has the form of particles dispersed in water, and several forms are conceivable for the xe2x80x9cconstraintxe2x80x9d of the particles with respect to the polysiloxane chains. In a first form, all or some of the polysiloxane chains are bundled inside the particles. In a second form, the ends of the polysiloxane chains are bundled inside the particles. In a third form, the polysiloxane chains are attached to the surface of the particles. The first to third forms all correspond to xe2x80x9cconstraintsxe2x80x9d, and also any mixture of the first to third forms corresponds to a constraint.
The backbone of the amphoteric urethane resin according to the present invention seems to constrain the polysiloxane compound (C). Therefore, while the polysiloxane chains have the quality of being relatively mobile, it seems that the polysiloxane compounds are relatively hard to separate from the amphoteric urethane resin. Consequently, at least one effect selected from improving the performance of paints, coating agents and cosmetics using the amphoteric urethane resin according to the present invention (for example, in the case of hair fixatives, properties such as the hair setting properties, the hair texture, the hair washing properties, and the hair touch, as well as the spreadability when applying the hair fixative) and improving the storage stability of the amphoteric urethane resin compared to conventional amphoteric urethane resins is achieved, and it is particularly superior in cosmetics.
It should be noted that the superior quality of the amphoteric urethane resin of the present invention is apparently due to these reasons, but the amphoteric urethane resin of the present invention is in no way limited by these reasons.